CN102791795B - Storage stable water based epoxy-amine curable systems - Google Patents
Storage stable water based epoxy-amine curable systems Download PDFInfo
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- CN102791795B CN102791795B CN201180013058.4A CN201180013058A CN102791795B CN 102791795 B CN102791795 B CN 102791795B CN 201180013058 A CN201180013058 A CN 201180013058A CN 102791795 B CN102791795 B CN 102791795B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
- C08G59/184—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0868—Osmium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
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Abstract
The invention relates to non aqueous curing agents for water dispersed epoxy resins. The curing agent composition offers a binder pot life of several hours, and in the presence of a metal, such as zinc, nearly no hydrogen generation is observed. The present curing composition can be mixed with a metal powder to provide a storage stable paste. The curing agent composition and/or paste is fully compatible with an epoxy water based resin. After low shear blending, the epoxy curing agent and metal system is storage stable for several hours working pot life that provides for cured coatings having good performance.
Description
Technical field
The present invention relates to the anhydrous solidifying agent for water-dispersed epoxy resin.On the one hand, the present invention relates to the solidifying agent being adapted at applying in water.
Background of invention
Be applied to the epoxy coating system that the solidifying agent based on polyamines solidifies the industry preparing multiple base material and keep coating and other protective coatings.Epoxy resin has excellent chemical-resistant.They also have good cementability for most of base material, such as, and various timber, wallboard, metal and brick masonry surface.Owing to having high resistance to fouling, be usually used in the epoxy amine system being rich in zinc.
Expect a kind of coating system containing low-down content of volatile organic compound (VOC) of preparation for a long time, as when there is no outside inhibitor or promotor, can applied in large temperature range and solidify.For the situation that there is zinc in water-based coating system, application person must solve the problem due to the reaction generation hydrogen between zinc and water.
The system of current many water-based epoxy resins and solidifying agent preparation is faced with the short problem of validity period.When there is metal such as zinc, for the system containing epoxy ingredient, curing agent component and metal, be even more difficult to obtain acceptable validity period.Need to provide a kind of solidifying agent for water-based coating system, it is compatible with epoxy ingredient, and when such as zinc exists metal, makes the generation of hydrogen reduce or at least remain on low-level.Therefore, need a kind of to there is the working life of expectation and the epoxy-resin systems of good base protection ability.Such coating system must possess the validity period of at least one work shift within the cycle; Namely 4-12 hour, preferably approximately 8 hours.
Summary of the invention
The invention provides a kind of curing agent composition, it provides the tackiness agent of several hours effectively its (4 to 24 hours), and when there is metal as zinc, generates hydrogen hardly.This curing agent composition comprises hardly containing the epoxy amine adduct of primary amine, there is the amine of wetting ability share price such as polyalkylene glycol, amine, there is polyamines or many amidoamines (polyamidoamine) of hydrophobic alkyl skeleton, hydrophobic hydrocarbon resinoid, wetting agent and silane derivative.Curing agent composition of the present invention can mix with metal-powder such as zinc to provide stable thickener.Curing agent composition of the present invention and/or thickener completely compatible with water-based epoxy resin.After low sheraing is blended, system can stably stored several hours (typically >4 hour).
The solidifying agent held except providing aqueous phase, this solidifying agent also should be easily compatible with water-based epoxy resin, to generate a kind of coating with good mechanics and corrosion resistance.Solidifying agent primary amine groups changes in these systems of secondary amine wherein, and balanced reaction problem that is active and validity period is more urgent.
Therefore need to obtain and there is water-compatible and the solidifying agent that the solidifying product with good mechanics and corrosion resistance is provided.
In one embodiment, the solidifying agent that can be used for epoxy resin of the present invention comprises:
(a) first amine adduct, it is the intermediate of amine end-blocking and the reaction product of monofunctional epoxy compound, wherein the intermediate of this amine end-blocking be by make each molecule of at least one have epoxy resin that the polyamines of at least 3 amine active hydrogen atoms or many amidoamines and at least one functionality be at least 1.5 with the mol ratio of epoxy functionalities equivalent and polyamines or many amidoamines for 0.9:1 to 1:10 reacts, and remove excessive polyamines or prepared by many amidoamines, and wherein said monofunctional epoxy compound exists with the amount being calculated as the primary amine reacted away in the intermediate being still present in this amine end-blocking,
B the second amine adduct that () is optional, it is prepared by cycloalphatic alkyl amine or polyamines and epoxy compounds;
(c) sterically hindered hydrophobic alkyl amine or diamines, or hydrocarbon resin;
(d) have amino or polyamino polyalkylene glycol moiety component and/or in by the time low-molecular-weight aminosilane, its medium viscosity optionally regulates with solvent such as alkylene glycol monoalkyl ether and alkylaryl ethanol, and,
E metal-powder that () is optional.
In another embodiment, the intermediate of amine end-blocking and the reaction product of mono-functional epoxy compound and said components (a) exist with the 2-15 weight percent (" wt% ") accounting for solidifying agent gross weight.
In another embodiment, the second optional amine adduct and said components (b), in use, to account for the 2-20wt% of solidifying agent gross weight, the amount of preferred 5-15wt% exists;
In another embodiment, sterically hindered hydrophobic alkyl amine or diamines and/or hydrocarbon resin and said components (c) account for the 2-30wt% of solidifying agent gross weight;
In another embodiment, said components (d), namely amino or polyamino polyalkylene glycol uses with the amount of 2-20wt%, and/or aminosilane uses with the amount of 3-10wt%, and wherein said wt% is with solidifying agent total weight.
Zinc is a kind of metal-powder that coatings industry is known, and obtains the preparation being rich in zinc, is used due to the corrosion resistance nature of its excellence on iron and steel.Based on the weight of wet coating material or application composition, zinc metal-powder typically exists with the amount of 15-80wt%, 30-75wt% or 50-70wt%; The coating used based on drying and solidify, it is 15-95wt%.
In another embodiment, solidifying agent of the present invention can be used for water-based epoxy resin preparation, and said preparation can be used for manufacturing coating, caking agent or sizing agent.
In another embodiment, solidifying agent of the present invention can be used for epoxy resin, and it is by following preparation:
(a) at least one per molecule is had epoxy resin that the polyamines of at least 3 amine active hydrogen atoms or many amidoamines and at least one functionality be at least 1.5 with the mol ratio of epoxy functionalities and polyamines or many amidoamines for 0.9:1 to 1:10 reacts intermediate to produce amine end-blocking, remove any excessive polyamines or many amidoamines, then make the intermediate of this amine end-blocking and monofunctional epoxy compound to be calculated as the quantitative response reacting away the primary amine existed in the intermediate of this amine end-blocking further, to prepare the first amine adduct
B second amine adduct is optionally added the first amine adduct of acquisition in step (a) to obtain amine adduct blend by (), described second amine adduct obtains by making cycloalphatic alkyl amine or polyamines and epoxy compounds reaction,
C () is by sterically hindered hydrophobic alkyl amine or diamines, and/or hydrocarbon resin adds in the first amine adduct of preparation in step (a), or adds in amine adduct blend prepared by step (b), to obtain the second blend,
(d) then by have amino or polyamino polyalkylene glycol moiety component and/or in by the time low-molecular-weight aminosilane add in the second blend obtained in step (c), to form the 3rd blend, and
E () optionally adds metal-powder in the 3rd blend.
Solidifying agent of the present invention as above, or its metal thickener are long-time stable.When these solidifying agent paste formulation, described long-time in almost do not record hydrogen and generate.
The acid of various types of aliphatics, cyclic aliphatic, modified fat and arylamine and their combination all can be used for the composition of solidifying agent.The example of the common subclass of fatty amine has such as polyoxy alkylidene, polyalkylene, fragrant acid amides (arylyl amine), ketoimine, cyanoethylation amine and the amine (mannich based amine) based on Mannich.The example of some modified fat acid has polymeric amide, polymeric amide/tetrahydroglyoxaline, amidoamines and amidoamines/tetrahydroglyoxaline.
In component (a), preferred polyamines comprises, such as m-xylene diamine, 1,3-bis aminomethyl hexanaphthene, 2-methyl isophthalic acid, 5-pentamethylene diamine, 1-ethyl-1,3-Malonamide, quadrol, diethylenetriamine (DETA), Triethylenetetramine (TETA) (TETA), polyoxypropylene diamine, 2,2 (4), 4-trimethylammonium-1,6-hexanediamine, isophorone diamine, 2,4 (6)-tolylene diamines, 1,6-hexanediamine, 1,2-diamino-cyclohexane and to amino double-hexyl methane (PACM).
For the preparation of the epoxy resin that the epoxy resin used in the component (a) of solidifying agent can be active arbitrarily, it has average at least 1.3 of each molecule, preferably 1.6 extremely preferred about 8 epoxy group(ing), most preferably 1, the 2-epoxy equivalent (weight) (functionality) of 3 to 5 epoxy group(ing).Epoxy resin can be saturated or undersaturated, straight chain or branching, aliphatic, cyclic aliphatic, aromatic or heterocycle, and can carry the substituting group of impact and reacting ethylene oxide in fact.Described replacement can comprise bromine or fluorine.Epoxy resin can be monomer or polymerization, liquid or solid, but under preferred room temperature is solid that is liquid or low melting point.Suitable epoxy resin comprises glycidyl ether, and it is prepared by making Epicholorohydrin carry out reacting under basic reaction conditions with the compound comprising at least 1.5 fragrant hydroxyls.Other examples being applicable to epoxy resin of the present invention comprise dihydroxy compound and diglycidyl ether, epoxy phenolics and cycloaliphatic epoxy resin.
Preferably, epoxy resin is the diglycidylether of dihydric phenol, the diglycidylether of hydrogenation dihydric phenol, aliphatic glycidyl ether, epoxy phenolics or cycloaliphatic epoxy resin.
The diglycidylether of dihydric phenol can react to prepare by such as making in the presence of base Epicholorohydrin and dihydric phenol.The example of suitable dihydric phenol comprises: two (4-hydroxyphenyl) propane (bisphenol-A) of 2,2-; Two (4-hydroxyl-3-tert-butyl-phenyl) propane of 2,2-; Two (the 4-oxybenzene phenol) ethane of 1,1-; Two (the 4-oxybenzene phenol) Trimethylmethane of 1,1-; Two (2-hydroxyl-1-naphthyl) methane; 1,5-dihydroxy naphthlene; Two (4-hydroxyl-3-alkyl phenyl) ethane of 1,1-etc.Suitable dihydric phenol can also be obtained (bisphenol-f) by phenol and aldehyde such as the reaction of formaldehyde.The diglycidylether of dihydric phenol comprises diglycidylether and the further product of dihydric phenol such as bisphenol-A of above-mentioned dihydric phenol, as United States Patent (USP) 3,477,990 and 4,734, mention in 468 those.
The commercial examples of preferred epoxy resin comprise EPON resin DPL-862,828,826,825,1001,1002, SU3,154,1031,1050,133,165, EPONEX resins 1510 etc.HELOXY properties-correcting agent comprises 32,44,48,56,67,68,71,84,107 and 505, and they all can derive from Momentive Specialty Chemicals Inc..Other commercial examples of epoxy resin comprise DEN 431,438, ERL-4221 ,-4289 ,-4299 ,-4234 and-4206, they all can derive from Dow Chemical Company.
The epoxide end-capping reagent used in component (b) can be connected to the aliphatics of epoxy-functional, alicyclic or aromatics.Make primary amine H-H reaction, decrease the chance that following situation occurs: the carbonate generated due to the carbonic acid gas in air and moisture and primary amine atomic reaction of hydrogen and carbamate, blush appears in coating and causes the coating chemical-resistant that differs from.Except reducing blush effect by making some or all primary amine groups on the arylamino polyamines of replacement react away, amino polyamines and epoxy-functional are reacted, also having the amine hydrogen making to dissociate has active in the advantage reacted with epoxy group(ing).But, the primary amine on amino polyamine compounds and epoxy functionalities are reacted, makes the secondary amine compound of end-blocking more compatible with epoxy resin.Therefore, can two-fold advantage be obtained, namely minimizing blush while, keep enough reactive behavioies and consistency, with at ambient temperature water existence and under there is no external catalyst combine and curing system.React with monoepoxide end-capping reagent and also can cause forming hydroxyl, this hydroxyl also may be used for reacting with other formation ether and/or the compound of ester.The epoxide of acrylated also can be used as end-capping reagent.
This type of primary amine end-blocking classification of epoxide comprises the unsaturated epoxy hydrocarbon of butylene, tetrahydrobenzene, epoxy styrene etc.; Monovalent alcohol is as the ether epoxy of methyl alcohol, ethanol, butanols, 2-ethyl butanol, dodecanol etc.; The epoxide with the alkylidene oxide adducts of the alcohol of at least 8 carbon atoms obtained by alkylene oxides base sequence being added to corresponding alkanol (ROH), such as commodity be called that NEODOL commercially sells those; The ether epoxy of unit price phenol, described unit price phenol such as phenol, cresols and adjacent, or contraposition by C
1-C
21other phenol that branching or nonbranched alkyl, aralkyl, alkaryl or alkoxyl group replace, such as nonylphenol; Monocarboxylic glycidyl ester, the glycidyl ester of the glycidyl ester of such as sad glycidyl ester, the glycidyl ester of capric acid, dodecylic acid, stearic glycidyl ester, arachic acid and the monocarboxylic glycidyl ester of the α described in United States Patent (USP) 3178454, α diallyl; The epoxy ester of unsaturated alcohol or unsaturated carboxylic acid, the glycidyl ester of such as neodecanoic acid, epoxyoleic acid methyl esters, the positive butyl ester of epoxyoleic acid, epoxidized palm oil acid methyl esters, epoxidation ethyl linoleate etc.; The acetal of phenylglycidyl ether, allyl glycidyl ether and glycidaldehyde.
The object lesson that can be used for the monoepoxide end-capping reagent of the present invention's practice comprises the alkyl glycidyl base ether having and have 1-18 carbons on hydrocarbyl chain, such as butyl glycidyl base ether or C
8-C
14the mixture of alkyl glycidyl base ether, cresyl glycidyl ether, phenylglycidyl ether, nonyl phenyl glycidyl ether, glycidyl ester to tert-butyl-phenyl glycidyl ether, 2-ethylhexyl glycidyl ether and neodecanoic acid.
Component (c) comprises sterically hindered amines or polyamines, the CORSAMINE DO that such as Corsacana Technologies (or CHEMOS GmbH Germany, Feixiang Chemicals, Akzo) provides.Component (c) also comprises hydrocarbon resin, the Piccolastic A5 that such as Eastman provides, the hydrophobicity Modaflow that Cytec provides, and/or the Disparlon L198X series that King Industry provides.
Curing agent composition comprises component (d) further, it can be the component with amino or polyamino polyalkylene glycol moiety, have medium to low molecular mass, JEFFAMINE T3000, T5000, T403 or D2000 of such as being provided by HuntsmanChemical Company, and/or the Trymeen 6607 that Cognis provides, and/or the ETHOX TAM-20 that ETHOX Chemicals provides.
Component (d) also comprises aminosilane, the Z-6020 that SILQUEST A 1120, the Dow Corning that such as Momentive Performance Materials Inc. provides provides, and/or the KBM-603 that ShinEtsu provides.
The viscosity of solidifying agent of the present invention is optionally by solvent adjustment, and described solvent is alkyl diol list propyl ether such as, such as, as 2-allyloxyethanol or alkylaryl alcohol, phenylcarbinol.Solvent can exist based on the amount of 0 to 80 % by weight of solidifying agent weight.
Solidifying agent of the present invention can be used for Curing Waterborne Epoxy Resin system effectively.The preferred embodiment of aqueous epoxy resins has, and based on the epoxy resin of bisphenol-A and/or bisphenol-f, it has the molecular mass between 350 to 10000, is dispersed in is with or without in the water of glycol ether co-solvent in nonionic mode.The commercial examples of aqueous epoxy resins comprises, such as, bisphenol-A resin, as EPI-REZ resin 3510-W-60 (emulsion), EPI-REZ 3520-WY-55, EPI-REZ3521-WY-53, EPI-REZ 6520-WH-53, EPI-REZ 3540-WY-55, EPI-REZ3546-WH-53 (dispersion), Araldite PZ756/67 (Huns tman), EPI-REZ resin 5522-WY-55, EPI-REZ resin 6530-WH-53 and similar dispersion.EPI-REZ resin 3510,3520,3521,3522,3540,3546,5522 and 6520 is provided by Momentive Specialty Chemicals Inc..Solidifying agent of the present invention is compatible with the aqueous dispersion not containing acid salt.These systems that can solidify contain water, one or more epoxy resin and one or more solidifying agent of the present invention.These aqueous epoxy resin systems that can solidify can further by commercially available Tertiary amine accelerators catalysis, and such as 2,4,6-tri-(dimethylaminomethyl phenol) or phenols solidify at a lower temperature.The EPIKURE solidifying agent 3253 that the example of this type of material has Momentive SpecialtyChemicals Inc. to provide or the DMP-30 that Rohm and Haas provides.
For aqueous epoxy resin systems, be with or without the Typical cure temperatures scope of promotor at 5 DEG C to 80 DEG C.These solidifying agent are typically for preparing the thermoset coating base material applied being had to good anticorrosive protection.The content of volatile organic compound of water-based epoxy resin preparation of the present invention, lower than 300g/l, preferably lower than 280g/l, more has preferably lower than 230g/l.
These aqueous epoxy resin systems can be used as and are applied to the coating of base material and the component of coating, described base material such as, metal, timber, glass and cement-bonded structure (cementatious structure).In order to prepare described coating or coating, by these resins and main raw material, swelling agent and anticorrosive pigment and optional additive such as tensio-active agent, defoamer, rheology modifier and scratch and anti-skidding reagent (mar and slip reagent).What the selection of these pigment and additive and consumption depended on coating draft application, and normally those skilled in the art understand.The water based epoxy compound of above-mentioned preparation and the moistening and dispersing property of amine polymer system can obtain stable painted coating formulation.
Solidifying agent of the present invention also can be used as the component use of caking agent, elastomerics, applying glue to fibers application.
the material used
EPON 828 is diglycidylether body epoxy resin, is provided by Momentive Specialty Chemicals Inc.
EPON 154 is diglycidylether liquid epoxiess, is provided by Momentive SpecialtyChemicals Inc.
TETA is Triethylenetetramine (TETA), and typical amines value is about 1436mg KOH/g, is provided by Dow Chemical.
DYTEK A is 2-Methyl pentyl diamines, and typical amines value is about 943mg KOH/g, is provided by Invista.
HELOXY Modifier 62 is ortho-cresol glycidyl ethers of commercial level, is provided by Momentive Specialty Chemicals Inc, and it is by making ortho-cresol process with Epicholorohydrin and sodium hydroxide.HELOXY Modifier is a kind of rare liquid, and its viscosity at 25 DEG C is 7 centipoises and its epoxy equivalent weights is about 175 to about 195.
CARDURA Resin E10 is the glycidyl ester of synthesis saturated monocarboxylic acid, is provided by Momentive Specialty Chemicals Inc.CARDURA E10 is a kind of rare liquid, and its viscosity at 25 DEG C is 7.1 centipoises and its epoxy equivalent weights is about 250.
EPI-REZ Resin 3520 (the aqueous epoxy resins dispersion of the diglycidylether of bisphenol-A, its EEW is 535g/eq), is provided by Momentive Specialty Chemicals.
EPI-REZ Resin 5522 (the modified aqueous epoxy resin dispersion of the diglycidylether of bisphenol-A, its EEW is 625g/eq), is provided by Momentive Specialty Chemicals.
EPON, CARDURA, HELOXY are the trade(brand)names of Momentive Specialty Chemicals.
testing method
ASTM
-D2196 viscosity, Brookfield viscosity
The consistence of-D562 coating, uses Stormer viscosity
-D3363 film hardness, uses pencil test
-D4366-95 pendulum hardness
The Volatility Levels of-D2369 coating
-D2369 measures the standard method of the Volatility Levels of coating
-D523 specular gloss transparent film
-D1308 household chemical product is to the effect of transparent and colored organic intensely processed products
-D5895 evaluates the drying of organic coating or the standard testing of film forming
The drying of coat under-D1640 room temperature, solidification and film forming
-B499D film thickness, uses mechanism
The non-destructive testing of-D1186 dry film thickness
The mandrel crooked test of-D522 adhering coating
-D1210-96Hegman, grinding fineness
-D3359 adhesive tape test measures cementability
-D2794 organic coating is to the tolerance of rapid deformation (shock)
The standard test of-B117-09 salt spray (atomization)
device
ISO 3682-96 acid number
granularity
The Brookhaven Bi-DCP particle size analyzer that the mensuration of emulsion and dispersion granule granularity is provided by Brookhaven Instruments Corporation or Beckman-Coulter LS instrument complete.Dn is number average diameter granularity, and Dw is the equal granularity of matter.All granularity datas adopt micron μ record.Unless otherwise indicated, herein to the said granularity of dispersion with Dn number average particle size record.
the weight (ASTM-D 1652-04) of every epoxide
The weight (WPE or EEW) of every epoxide of all products measures in the following manner: by making the sample drying through weighing with methylene dichloride component distillation, then correct percent solids with currently known methods titration residue, thus measure the WPE under 100% solid content.
amine value
Be defined as the KOH milligram number being equivalent to basic nitrogen content in 1 gram of sample, it is measured by acid base titration.
amine equivalent weight
Be defined as and the weight needed for the epoxide reaction of monovalent weight, measured by the known stoichiometry of reactant in the amine nitrogen content in Momentive testing method HC-715-88 and products therefrom, described products therefrom contains nitrogen, described nitrogen have by ambient conditions with epoxide reactive active hydrogen.
Embodiment
Embodiment 1 solidifying agent of the present invention
Embodiment 2 solidifying agent of the present invention
Embodiment 3 solidifying agent of the present invention
Formulation for coating material (transparent)
Embodiment a)
Embodiment b)
Viscosity measurement procedure
With scuppit, solidifying agent+Eastman EP or water are mixed, add the epoxy resin of stoichiometric ratio, mix 5 minutes further with scuppit.
With Krebs Unit 23 DEG C at t=0 time measure viscosity, and per hourly all to measure, until 8 hours.
EPIKURE 8290/EPI-REZ 3520
| Time | 50% solid |
| 30 minutes | 101KU |
| 2 hours | Viscosity goes beyond the scope |
| 3 hours | Almost gel |
Solidifying agent 1/EPI-REZ 3520
| Time | 50% solid |
| 30 minutes | 85KU |
| 7 hours | 82KU |
Solidifying agent 2/EPI-REZ 3520
| Time | 50% solid |
| 30 minutes | 55KU |
| 2 hours | 57KU |
| 7 hours | 55KU |
| 3 days | 54KU |
With EPI-REZ 3520/EPI-REZ 3540 resin blend test solidifying agent 1 in the priming paint being rich in zinc.In 28 hours periods also tested viscosity
500 μm of DFT, use shaft-like applicator to apply
The solidifying agent of embodiment 1 is also tested following being rich in the priming paint of zinc.
At 23 DEG C, the hydrogen that part A discharges negligible (deposit in the PE bottle closed and raise without pressure for >3 month), not there is bubble in thickener.
At 23 DEG C, the compo A+B of solidifying agent 1 and EPI-REZ 3521 is in application validity period and be even up to 11 days all without obvious air release.Compared with EPIKURE solidifying agent 8290 and EPI-REZ 5522 (water-based epoxy resin), there is the generation of hydrogen in said composition of the present invention hardly.As mentioned above, the system with EPI-REZ 3520 and EPIKURE 8290 can not enough stably use (after being no more than 2 hours gel).
The air release that solidifying agent 1/EPI-REZ 3521 is considerably less, without visible bubble in bubble, even if after 11 days.
EPIKURE 8290/EPI-REZ observed bubble after 5522,24 hours, at 23 DEG C, observe strong air release.
EPIKURE 8290/EPI-REZ 3520, (as comparing) foams immediately at 23 DEG C.
Same priming paint is applied over sandblasting steel SA2.5 (for erosion resistance test) and QD plate (for dry and tapering spindle test).Be exposed to the anticorrosive protection of salt fog condition after lower 1000 hours outstanding (DFT=30-40,50-70 micron, cross hatching and panel area are without obvious corrosion).Drying (passing through thumb) under 20-30 micron reached in 15-30 minute.Successfully pass tapering spindle test (flawless).
In order to accelerate drying further, allocate priming paint by regulating solubility promoter.QD plate has 20-30 micron DFT, at 23 DEG C, be no more than 10 minutes reach drying.
With the priming paint (see following) of epoxy resin (type-1) dispersion white with solidifying agent 1.When this system is directly applied to metal (SA2.5), exposes in salt mist environment after 1000 hours and there is excellent anticorrosive result, even if priming paint is used (long validity period) after the induction of 7 hours.
Same white primer is applied over being rich on the priming paint of zinc based on same binder system as top coat.Be applied on sandblasting steel SA2.5 by the priming paint being rich in zinc with 30 microns of DFT, at 23 DEG C, drying is less than 10 minutes, then applies white coating with 50 microns of DFT, obtains amounting to the coating of about 80 microns of DFT.Whole coating is solidified 20 minutes at 70 DEG C, then solidifies 2 weeks at 23 DEG C.After 1000 hours salt sprays, cross hatching or face do not have visible corrosion.After being immersed in the water 500 hours, maintain excellent adhesiveness between layers: the source, interface of two layers of coatings or not inefficacy between priming paint and substrate.
Above-mentioned experimental data clearly shows, the solidifying agent of the present invention combined with reactive epoxies dispersion such as EPI-REZ3521, can be used as transparent, the painted aqueous based systems stably stored being rich in zinc several hours.
Claims (13)
1., for the solidifying agent of epoxy resin, comprise:
(a) first amine adduct, it is the intermediate of amine end-blocking and the reaction product of monofunctional epoxy compound, wherein the intermediate of this amine end-blocking be by make each molecule of at least one have epoxy resin that the polyamines of at least 3 amine active hydrogen atoms or many amidoamines and at least one functionality be at least 1.5 with the mol ratio of epoxy functionalities equivalent and polyamines or many amidoamines for 0.9:1 to 1:10 reacts and prepare, wherein remove excessive polyamines or many amidoamines, and wherein said monofunctional epoxy compound exists with the amount being calculated as the primary amine reacted away in the intermediate being still present in this amine end-blocking,
B the second amine adduct that () is optional, it is prepared by cycloalphatic alkyl amine or polyamines and epoxy compounds;
(c) sterically hindered hydrophobic alkyl amine or diamines, hydrophobic hydrocarbon resinoid, or more both;
D () has the component of amino or polyamino polyalkylene glycol moiety, in by the time low-molecular-weight aminosilane, or more both, and,
E metal-powder that () is optional.
2. the solidifying agent described in claim 1, it comprises (a) of the 2-15% based on described solidifying agent weight.
3. the solidifying agent described in claim 1 or 2, wherein this solidifying agent comprises second amine adduct (b) of 2-20wt%, and described wt% is based on the weight of described solidifying agent.
4. the solidifying agent described in claim 1 or 2, comprises (c) of 2-30wt%, and described wt% is based on the weight of described solidifying agent.
5. the solidifying agent described in claim 1 or 2, wherein:
(i) when the compound of (d) be amino or polyamino polyalkylene glycol moiety time, described solidifying agent comprises this amino or the polyamino polyalkylene glycol moiety of 2-20wt%;
(ii) when the compound of (d) is aminosilane, this solidifying agent comprises this aminosilane of 3-10wt%;
(ii) when this solidifying agent comprise be the amino of (d) or polyamino polyalkylene glycol moiety and aminosilane time, this amino or polyamino polyalkylene glycol moiety are the 2-20wt% of described solidifying agent, and this aminosilane is the 3-10wt% of described solidifying agent
Described wt% is based on the weight of described solidifying agent.
6. solidifying agent according to claim 1, wherein said metal-powder exists and comprises zinc.
7. a water-based epoxy resin preparation, it comprises the solidifying agent described in any one of claim 1-5.
8. water-based epoxy resin preparation according to claim 7, wherein this water-based epoxy resin formulation characteristics is that content of volatile organic compound is lower than 300g/l.
9. the purposes of the water-based epoxy resin preparation described in claim 7 or 8 in coating, binding agent or applying glue application.
10. coating or an application composition, it comprises:
Water-based epoxy resin preparation described in claim 7 or 8; With
The zinc metal-powder of 15-80wt%, the weight of this zinc metal-powder wt% coating based or application composition.
11. comprise water-based epoxy resin preparation according to claim 7, or the solidifying product of coating according to claim 10 or application composition.
12. methods preparing solidifying agent, comprising:
(a) at least one per molecule is had epoxy resin that the polyamines of at least 3 amine active hydrogen atoms or many amidoamines and at least one functionality be at least 1.5 with the mol ratio of epoxy functionalities equivalent and polyamines or many amidoamines for 0.9:1 to 1:10 reacts intermediate to produce amine end-blocking, remove any excessive polyamines or many amidoamines, then make the intermediate of this amine end-blocking and monofunctional epoxy compound to be calculated as the quantitative response reacting away the primary amine existed in the intermediate of this amine end-blocking further, thus preparation the first amine adduct
B second amine adduct is optionally added the first amine adduct of acquisition in step (a) to obtain amine adduct blend by (), described second amine adduct reacts by making cycloalphatic alkyl amine or polyamines and epoxy compounds and obtains,
C () is by sterically hindered hydrophobic alkyl amine or diamines, hydrophobic hydrocarbon resinoid, or more during both add in step (a) the first amine adduct, or add in the amine adduct blend of step (b), to obtain the second blend
D () will have the component of amino or polyamino polyalkylene glycol moiety further, in by the time low-molecular-weight aminosilane, or more both add in the second blend obtained in step (c), to form the 3rd blend, and
E metal-powder is optionally added the 3rd blend by ().
13. 1 kinds of coating or application composition, it comprises:
Water-based epoxy resin preparation described in claim 7 or 8; With the zinc metal-powder of 15-95wt%, this metal-powder wt% applies based on drying and the weight of the coating solidified.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP10002471.0 | 2010-03-10 | ||
| EP10002471A EP2365015A1 (en) | 2010-03-10 | 2010-03-10 | Storage stable water based epoxy-amine curable systems |
| PCT/US2011/027200 WO2011112452A1 (en) | 2010-03-10 | 2011-03-04 | Storage stable water based epoxy-amine curable systems |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102791795A CN102791795A (en) | 2012-11-21 |
| CN102791795B true CN102791795B (en) | 2015-01-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180013058.4A Active CN102791795B (en) | 2010-03-10 | 2011-03-04 | Storage stable water based epoxy-amine curable systems |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US9221959B2 (en) |
| EP (2) | EP2365015A1 (en) |
| KR (1) | KR101447794B1 (en) |
| CN (1) | CN102791795B (en) |
| AU (1) | AU2011224629B2 (en) |
| BR (1) | BR112012022683B1 (en) |
| CA (1) | CA2790837C (en) |
| DK (1) | DK2545121T3 (en) |
| ES (1) | ES2601248T3 (en) |
| PL (1) | PL2545121T3 (en) |
| RU (1) | RU2533142C2 (en) |
| WO (1) | WO2011112452A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2692778A1 (en) | 2012-07-31 | 2014-02-05 | Momentive Specialty Chemicals Research S.A. | Epoxy resins and silane aqueous co-dispersions and the uses thereof |
| US10611876B2 (en) | 2014-04-04 | 2020-04-07 | Daicel Corporation | Epoxy-amine adduct, thermoplastic resin composition, sizing agent, sizing agent coated carbon fiber, and fiber-reinforced composite material |
| WO2017161534A1 (en) | 2016-03-24 | 2017-09-28 | Ticona Llc | Composite structure |
| EP3710508B1 (en) | 2017-11-19 | 2023-08-16 | Allnex Austria GmbH | Hardener composition for aqueous epoxy resin based coating compositions, process for its preparation and use thereof |
| RU2704010C1 (en) * | 2019-07-16 | 2019-10-23 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Ивановский государственный химико-технологический университет" | Method of producing a pigmented aminophenol curing accelerator - modifier of epoxy composite materials |
| TWI705083B (en) * | 2019-11-13 | 2020-09-21 | 南亞塑膠工業股份有限公司 | Curing agent composition and curing agent coating formula thereof |
| CN112625629B (en) * | 2020-12-02 | 2022-06-10 | 上海牛元工贸有限公司 | Low-odor, low-VOC and low-sensitization seam beautifying agent and preparation method thereof |
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| CN1278844A (en) * | 1997-11-13 | 2001-01-03 | 国际壳牌研究有限公司 | Water compatible curing agents for epoxy resins |
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| BE857754A (en) * | 1976-08-18 | 1978-02-13 | Celanese Polymer Special Co | COMPOSITION OF RESIN FOR COATINGS, ESPECIALLY BY CATHODIC ELECTRODEPOSITION |
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| US4605690A (en) * | 1985-04-15 | 1986-08-12 | Inmont Corporation | Low volatile organic content cathodic electrodeposition baths |
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| RU2028320C1 (en) * | 1991-04-18 | 1995-02-09 | Концерн "Хлорвинил" | Curing agent for epoxy resins and method for its production |
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2010
- 2010-03-10 EP EP10002471A patent/EP2365015A1/en not_active Withdrawn
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2011
- 2011-03-04 WO PCT/US2011/027200 patent/WO2011112452A1/en active Application Filing
- 2011-03-04 CN CN201180013058.4A patent/CN102791795B/en active Active
- 2011-03-04 AU AU2011224629A patent/AU2011224629B2/en active Active
- 2011-03-04 US US13/580,568 patent/US9221959B2/en active Active
- 2011-03-04 CA CA2790837A patent/CA2790837C/en active Active
- 2011-03-04 RU RU2012143200/05A patent/RU2533142C2/en active
- 2011-03-04 BR BR112012022683-5A patent/BR112012022683B1/en active IP Right Grant
- 2011-03-04 PL PL11753841T patent/PL2545121T3/en unknown
- 2011-03-04 EP EP11753841.3A patent/EP2545121B1/en active Active
- 2011-03-04 DK DK11753841.3T patent/DK2545121T3/en active
- 2011-03-04 KR KR1020127025456A patent/KR101447794B1/en active IP Right Grant
- 2011-03-04 ES ES11753841.3T patent/ES2601248T3/en active Active
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| US5508324A (en) * | 1995-08-14 | 1996-04-16 | Air Products And Chemicals, Inc. | Advanced polyamine adduct epoxy resin curing agent for use in two component waterborne coating systems |
| CN1278844A (en) * | 1997-11-13 | 2001-01-03 | 国际壳牌研究有限公司 | Water compatible curing agents for epoxy resins |
Also Published As
| Publication number | Publication date |
|---|---|
| US9221959B2 (en) | 2015-12-29 |
| BR112012022683A2 (en) | 2018-05-08 |
| EP2365015A1 (en) | 2011-09-14 |
| CA2790837A1 (en) | 2011-09-15 |
| WO2011112452A1 (en) | 2011-09-15 |
| PL2545121T3 (en) | 2017-01-31 |
| BR112012022683A8 (en) | 2018-06-12 |
| EP2545121B1 (en) | 2016-08-24 |
| RU2533142C2 (en) | 2014-11-20 |
| KR101447794B1 (en) | 2014-10-06 |
| CA2790837C (en) | 2015-11-03 |
| BR112012022683B1 (en) | 2020-05-12 |
| CN102791795A (en) | 2012-11-21 |
| AU2011224629A1 (en) | 2012-09-27 |
| RU2012143200A (en) | 2014-04-20 |
| EP2545121A1 (en) | 2013-01-16 |
| US20130072597A1 (en) | 2013-03-21 |
| ES2601248T3 (en) | 2017-02-14 |
| EP2545121A4 (en) | 2015-10-07 |
| DK2545121T3 (en) | 2016-11-28 |
| KR20120139758A (en) | 2012-12-27 |
| AU2011224629B2 (en) | 2014-02-13 |
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